Method of making photographic relief images



March 13, 1951 w, N DEUSEN 2,544,905

METHOD OF MAKING PHOTOGRAPHIC RELIEF IMAGES Filed Oct. 23, 1948 EXPOSURE SENSITIVE LAYER 0F POLYMER/C J 1W4 MATERIAL ANDALKETO/VE JENS/T/ZER W film 50LVENT DEVELOPMENT w/yjy JOA REMOVING RES/S 7' WERTER R VAN DE USEN INVENTOR ATTORNEY ('7' AEIENT cation in the photomechanical art.

Patented Mar. 13, 1951 2,544,995 FlCE METHOD OF MAKING PHOTOGRAPHIC RELIEF DVIAGES Werter P. Van Deusen, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application October 23, 1948, Serial No. 56,174

8 Claims. 1

This invention relates to methods of making photographic relief images of particular use in the photomechanical arts.

It is well known in the art of photomechanical reproduction to utilize various materials such as bichromated shellac or glue for forming resist images upon various supports such as metal plates. The support is then etched or otherwise treated in the areas not covered by the resist image and the resultant image, usually after the removal of the resist image, is used for printing. One method of forming relief images on metal supports is disclosed in the Beebe et al. U. S. Patent 1,587,274, granted June 1, 1926, includes coating a metal support with an alketone condensation product resulting from the reaction of, for example, furfural with acetone, which coating is light-sensitive and after exposure under an image is treated with a solvent which removes the coating in the unexposed regions of the support. Subsequently, the support is etched in the regions from which the light-sensitive coating has been removed. A number of alketone compounds have been proposed for such usage, such as monoalketones; for example, benzal acetone, chalconesj for example, cinnamal acetophenone, dialketones;, for example, difurfural'acetom and a cyclic dialketone, difurfural cyclohexanone. I have found that such light-sensitive alketone compounds have limited use but when combined with a polymeric material of the type to be described, they furnish resist layers having a wide appli- One object of my invention is to provide a method of making photographic relief images by means of alketone light-sensitive resist materials. Another object of my invention is to provide alketone materials which are light-sensitive and adapted to selective development. Other objects of my invention will appear from the following description.

The objects of my invention are accomplished in part by coating a support with a layer of a mixture of certain alketone compounds and a polymeric material such as cellulose ethyl ether or an acrylate resin such as methyl methacrylate resin and after exposure of the layer under a line or halftone image, selectively removing the unexposed area of the layer by means of a hydrocarbon solvent. In addition to the polymeric materials mentioned, cellulose nitrate and polystyrene resin may be used in combination with the alketone compound as well as otheracrylate resins such as methyl acrylate, polyvinyl acetates, polyvinyl chloride-acetates, polyvinyl acetals, coumarone-indene resins, rosin modified ma eic ester resins, chlorinated paraffins, polyisobutylenes. chlorinat d rubbers and urea and pheno ic resins. However, cellulose ethyl ether and methyl methacrylate resin represent preferred embodiments of the polymeric materials useful in my invention, since these polymeric materials furnish resistimages of "the highest definition and provide the best resistance to etching solutions and other treatments applied to etch the bared areas of a photomechanica'l support. H v

The alketone compounds .forminga part of my invention havelthe general formula;

R.OH= C .-g.9=CH- R wherein R represents a furfuryl, styryl, or'aryl group of the benzene series, X represents the atoms necessaryto complete a cyclic'ring of five or six carbon atoms. Examples of such compounds fallin'g'within the above general formula are the alketone condensates obtained by 're=- action or cinnamic aldehyde, anisaldehyde or furfuraldehyde with cyclopentanone, p-methyl cyclohexanone or cyclohexanone. Of these alketone condensates I have found difurfural cyclepentanone to' be most useful and most generally applicable whenemployed with cellulose ether or a resin to a wide range of photomechanical processes. Accordingly, a composition containing a mixture of difurfural cyclopentanone and cellulose ethyl ether having hydrocarbon solubility, the ether being well etherified' to the extentof about 50% ethoxyl, represents compositions from which light-sensitive coatings yielding the best relief images can be obtained.

The amount of alketonecondensate used in the resist is determined by its solubility in "the polymeric constituent in the dry state, and generally '6-12% alketoneis satisfactory although this value will vary somewhat with the particular polymeric constituent selected.

v The accompanying drawings illustrate in enlarged cross-sectional view, the appearance of materials and the various steps in my process 'of producing photogra hic relief images in the manner of my invention.

The following examples are illustrative of my invention and describe it with particular refer ence to the accompanying drawings:

, Example 1 The light-sensitive co positions above-dc scribed are particularly useful in the reparation of etched co er or zinc hal tone lates substituting 'my alketone com ositions for the conventional bichromaterl glue and she lac used for this afiectsafthe .characteristics of the *plate and distorts the tone reproduction of the halftone image. Following this the resist image is normally re"- moved by scrubbing in a hoticoncentrated-alkali solution. According to the simplified process of my invention, the copper,.plateisnoated.vwith a sensitive mixture of the followingcomposition:

Polymethylmethacrylate -grams- 7125 Difurfuralcyclopentanone ;do .273 Crystal Violet carbinol base do :.86 Chlorobenzene cc 80-100 Toluene cc 20%) ,;.After"drying*the coating it' is exposedundera ihalftone image and the resistxdeveloped' by treat- "ing'theexposed-plate-With a-mixture OfB-lO-parts .xylene and 2-() parts toluene. Other suitable'sol- Wents includeibenzene, chlorobenzena-oand pchlorotoluenefdi isopropyl ketone; cyclohexanone and isophorone. The hydrocarbon developer removes the coating. in the unexposed region of the plate, following which the plate is etched in 40-46 Be. ferric chloride solution and the conventional fhurning fin. step may :be omitted. fluringzthe:etchingstepxtheresist remains trans- :parent: ands-thesdegreei of undercutting randsside .-action:;:cambe readily vobserved .and scrubbing-of iithepplate vtorremovezoverhang:may: .be. dispensed with. when: the retchi-ngs-is .-complete,-. thetresist maycbecremoved by-washingchr arsolvent such -as acetone. 'Thissmethod of. utilizing the-sensitive oompositionsof the-invention-is. illustrated-zinthe drawings according. to which isshownexposure of rasscnsitiveeelementihaving; a--.sup.port such as ,a cco'pper pplate 4 flwarryingrthe. sensitive layer PH 101 rthe1.-invention,'-.-to --.sub' ect 4 2 having .opaque image areasl3 ,cpreferably when. in :vacuumcon- "tact. .-.Duringi-solvent .development the unexposed areas .of :"sensitive layer .1 l .of .the .-.element.-are removed "leaving, the ..support bared in the unexposed areas -I4wand -.-the remaining areas .15 (it-layer. l l-.:constitute-.a:resist. Subsequentetchingtwith, for example. ferric-chloridesolution removes the support :inthau-nexposed areas l 4 -and when .the resist is i removed, aprinting. plate; re- :sults: having. etched..-i-mage areas .16 in the ..un- ,zexposed-aareas of thewriginaL coppen-platessupport. 10.

F EwampZe- Z Substantial improvement .of uality results from-electroplating .a .-chrom-ium..1ine .or. halftone image or .copper cplates .if the. conventional bichromated shellac resist ..is \substituted ..by .an photosensitive resist .of my. invention. A light=sensitive layeris coatedon tozacopper, .plate from the following-composition:

.Aiter drying the coating, the .plate is;printed under, ailine .or halftone image and developed bycswa'bbing in a fatty acid. developer of the following composition.

- Grams Myristioacid .300 Ligrom .(B.- P. -90-.1-20. C

.Thehy drocarbon solution of fatty acid used as a deveoper removes the sensitive layer in the uneexposed region. If desired, other fatty acids may nbesnsed inplaceof myristic acid in the developer :5 asolution; for example, saturated fatty acids havingastraight carbon chain of from 11 to 15 carbonnatoms; .for-example, lauric or palmitic acids ..and;in.-the latter case of 9% solution in ligroin gives excellent results. After development of theresist'image'the plate is degreased, baked and-preferably dipped in five per cent nitric acid solution to remove oxide from the surface. The plate -:is 1 .then-.:e1ectroplated:.:for from: aboutttwo .to .founminutesmt. -.a.:currentc density of: two. 1 ampere per square inch-.at sixntoweightwolts the plating .bath .being maintainedwat. 100410 .105" F. :and being. .composed;of a.-solution of.250 grams .ofchromic: acid and 2.5 grams of sodium: sulfate 1orrsulturicracidgper-liter. -A sheet of leadis used .as an :anode. vFollowing .formation of the bimetallic printing: plate, the e resist image may .be removed witha solvent. such-as acetone.

.In .:contrast to Y the conventional .Joichromated shellaossensitive coatings-used.in thevabove and ..-followingexamples, the. alketone coating haslan important -=advantage: lying in .the: fact that. its .sensitivity is u-nafiectedbystorage .in the. dark .and itrisQnot susceptible to changesvinuatmospheric -:conditions. 30

.flhe .light-sensitive alketone ..compositions -0: -the inventionmay .be .usedfor .forming-.a=.r elief .image ona support and etchinglthe .supportlby meansrof sandblasting. .Accorldingto' thevariation ofthe invention a support such. as :ametal .or,,glass .plate, is, preferablyffirst coated with a friable layer ,o'tresin. containing .a pigment like barytes, then witha-thin layer oia water-glass solutionffollowed .loyw a thin. layer of natural or synthetic rubber deposited from solvent medium, such asaJoenzene solution .of..neoprene. lFollow- .ing this, .a idyed solution of an alketone composition; for example, .of formulagiven' in Example '2,.is coated on tothe plate, exposedto'a line orhalftone image and the resist image. 'developed by treatment 'in.a"fatty acid ldeveloper solutionsuch asgiven infExample '2. Theplate thusiprovided with" a resist image is thensandblasted with "700 mesh femery "powder using a pressure. of about 20 pounds per square inch. If the neoprene subcoating is omitted from the aboveplate, the air pressure used for sandblasting should be of theorder of less than IOpounds 0 .per -square inch. The cellulose ethyl ether .present'in the sandblastresist.improves the resistance to shockby'ithe' sandblast particles.

Example?! The .-.light=sensitive alketone hcompositionaof the invention may besused ion-forming hydrol-ized-cellulose estenprinting plates. A- sheetof =well-.-.esterif1ed .cellulose: acetate .or. .a. mixed. ester .of:.cellulose eSllCh' as .cell-ulose..acetate-propionate .is :hydrolized with -:a five .per .cent solution-of sodium. hydroxide! :i-n.-50 per. .cent. ethylalcohol. so .as-v tor-produceassurface hydrolysis. on. the. .sheet to a :depth of approximately 0.5 .micron. After washing and dryingthesheet, a sensitive alketonecomposition such. as. provided in. Examplez is coated onatheahydrolized surface of the cellulose .ester-z sheet-.a-nd dried in-...the-..us.ual manner. After :exposure of=the sensitive-layeritora lineor halftone. image, the element developed. in .a 75 fatty..a.cid developersof the=type provided above containing myristic acid in petroleum naphtha, then the element is treated so as to remove the stratum of hydrolized cellulose acetate in the region not covered by the alketone resist. This may be accomplished by subjecting the sheet to a sandblast using 500 mesh emery powder and an air pressure of 20 pounds per square inch. After removal of the alketone resist an image of high resolving power is obtained.

It will be apparent from the above examples that the use of alketone sensitized compositions of my invention in place of conventional materials, greatly simplifies photomechanical methods of reproduction of subjects by means of line or half-tone methods. Also, aside from simplicity and increased speed of operation being made available, the invention provides for improvements in quality of reproductions.

My invention having been described I would have it understood that the disclosure herein is by way of example and that I consider as included in my invention all modifications and equivalents falling within the appended claims.

What I claim is:

1. The method of making a photographic relief image which comprises coating a support with a layer of a mixture of a polymeric material selected from a group consisting of cellulose ethyl ether and acrylate resins, and a light-sensitive alketone compound having the general formula:

where R represents a member selected from a group consisting of furfuryl,-styryl and an aryl group of the benzene series, X represents the atoms necessary to complete a cyclic ring of from five to six carbon atoms, forming a relief image in said layer by exposure to an image and washing away the unexposed area of said layer with a solvent for only said area.

2. The method of making a photographic relief image which comprises coating a metal plate with a layer of a mixture of cellulose ethyl ether and difurfural cyclopentanone, forming a relief image in said layer by exposure to an image and Washing away only the unexposed area of said layer, and etching said metal plate with ferric chloric solution in the areas bared by said washing step. 1

3. The method of making a photographic relief image which comprises coating a rigid support with layers first of water glass, rubber, and then a sensitive layer of a mixture of cellulose ethyl ether and difurfural cyclopentanone, forming a relief image in said sensitive layer by exposure to an image and washing away only the unexposed area of said layer, and subjecting the resultant product to a sandblast to etch said support in the areas bared by said washing step.

4. The method of making a photographic relief image which comprises coating on a prehydrolyzed surface of a cellulose ester support a layer of a mixture of cellulose ethyl ether and difurfural cyclopentanone, forming a relief image in said layer by exposure to an image and washing away only the unexposed area of said layer, and subjecting the resultant product to a sandblast to etch said support in the areas bared by said washing step.

5. The method of making a photographic relief image which comprises coating a support with a layer of a mixture of cellulose ethyl ether and a light-sensitive alketone compound having the general formula:

0 RCH=C C=CH-R I I \x/ where R represents a member selected from a group consisting of furfuryl, styryl and an aryl group of .the benzene series, X represents the atoms necessary to complete a cyclic ring of from five to six carbon atoms, forming a relief image in said layer by exposure to an image and washing away theunexposed area of said layer with a solvent for only said area.

7. The method of making a photographic relief image which comprises coating a support with a layer of a mixture of a polymeric material selected from a group consisting of cellulose ethyl ether and acrylate resins, and a light-sensi tive alketone compound having the general formula:

o RCH=Qg$J=CH-R \\X:

where R. represents a member selected from a group consisting of furfuryl, styryl and an aryl group of "the benzene series, X represents the atoms necessary to complete acyclic ring of from five to six carbon atoms, forming a relief image in said layer by exposure to an image and washin away the unexposed area of said layer with a solvent for only said area, and subjecting the resultant product to a sandblast to etch the support in the areas bared by said washing step.

8. The method of making a photographic relief image which comprises coating a metal plate with a layer of a mixture of a cellulose ethyl ether and an alketone compound having the general formula:

where R represents a member selected from a group consisting of furfuryl, styryl and an aryl WERTER P. VAN DEUSEN. No references cited. 

1. THE METHOD OF MAKING A PHOTOGRAPHIC RELIEF IMAGE WHICH COMPRISES COATING A SUPPORT WITH A LAYER OF A MIXTURE OF A POLYMERIC MATERIAL SELECTED FROM A GROUP CONSISTING OF CELLULOSE ETHYL ETHER AND ACRYLATE RESINS, AND A LIGHT-SENSITIVE ALKETONE COMPOUND HAVING THE GENERAL FORMULA: 